Metal monoazo dyestuffs



United States Patent 7 Claims. 01. 260-145) ABSTRACT OF THE DISCLOSUREComplex metal dyestuffs having, in the form of the free acids, theformula in which D is a benzene or naphthalene diazo component, A is anaphthalene, pyrazolone or acetoacetylaminobenzene azo component, X ishydroxyl or carboxyl in orthoposition to the azo-linkage, Y is hydroxylor amino in ortho-position or in vicinal position to a carbon atomattached to the azo linkage, R is hydrogen or lower alkyl, Me ischromium or cobalt, n and m stands for 1 or 2, and m stands for 0, 1 or2.

The present invention relates to complex metal dyestuffs and toprocesses for their manufacture; in particular, it relates to complexmetal dyestuffs which-in the form of the free acidshave the generalformula in which D represents the radical of a diazo component of thebenzeneor naphthalene-series, A represents the radical of an azocomponent, X represents a hydroxyl or carboxyl group bound inortho-position to the azo-linkage, Y represents a hydroxyl or aminogroup bound in ortho or in vicinal position to a carbon atom attached tothe azo linkage, R represents a hydrogen atom or an alkyl group, Merepresents chromium or cobalt and n as well as m represent 1 or 2, and mstands for 0, 1 or 2.

It has now been found that valuable metalliferous azodyestuffscontaining two dyestuff radicals per metal atom in complex bound form,are obtained by (a) treating a metallizable azo-dyestuff which-in theform of its free acid-has the general formula in which D represents theradical of a diazo component of the benzeneor naphthalene series, Arepresents the radical of an azo component, X represents a hydroxylorcarboxyl group bound 'in ortho-position to the azolinkage, Y representsa hydroxyl or amino group. bound in ortho-, R represents a hydrogen atomor an alkyl group and n as well as m represents 1 or 2, a mixture of twoazo-dyestuffs of the Formula I mentioned above, or a mixture of anazo-dyestuff of the same Formula 1 and of another metallizableazo-dyestuif, with metal-yielding agents, preferably, with agentsyielding cobalt or chromium,

(b) reacting a metallizable azo-dyestuif of the abovementioned Formula 1with a complex metal compound of an o.o'-dihydroxy-azo-dyestuff or an0-hydroxy-oamino-azo-dyestuff containing a metal atom, preferably, achromium atom per dyestutf molecule in complexbound form, in the molarratio of about 1:1,

(0) reacting simultaneously or successively a metallizable azo-dyestufiof the general formula in which D, A, X, Y, R, n and m have theabove-mentioned meanings and Z represents a halogen atom, a mixture oftwo azo-dyestuffs of the above Formula 2 or a mixture of an azo-dyestuflof the above Formula 2 and another metallizable aZo-dyestuff, with saltsof the thiosulfuric acid and metal-yielding agents, preferably, agentsyielding cobalt or chromium, or

(d) reacting 2:1-comp1ex metal compounds of azodyestutfs, preferably,such of cobalt or chromium containing one or two dyestuffs of the aboveFormula 2 per molecule, with salts of the thiosulfuric acid.

The groupings D and A used in the above-mentioned Formulae 1 and 2, cancarry any substituent desired. As examples there are mentioned halogenatoms such as atoms of chlorine or of bromine, nitrocyanoor acylaminogroups such as acetylamino-, benzoylaminoor carbomethoxy-amino groups,unsubstituted or substituted alkyl groups such as methyl-, ethylortrifluoromethyl groups, furthermore, alkoxy groups such as methoxyorethoxy groups, alkyl-sulfoxide groups or alkyl-sulfonyl groups such asmethyl sulfonyl-, ethylsulfonyland propylsulfonyl groups, as well asgroups imparting solubility in water, such as sulfonic acid groups orcarboxylic acid groups, furthermore, sulfonic acid amide groups, -N-substituted sulfonic acid amide groups such as N-methyl sulfonic acidamide groups, N-B-hydroxyl-ethyl-sulfonic acid amide groups andN.N.disubstituted sulfonic acid amide groups such asN.N-dimethyl-sulf0nic acid amide groups, N.N-diethyl-sulfonic acid amidegroups or N.N- di-(,S-hydroxyethyl)-sulfonic acid amide groups.

The metal-free azo-dyestuffs of the above-mentioned Formula 1 can beprepared by combining diazo compounds of the benzeneornaphthalene-series, which contain a hydroxy group, or a carboxy group ora hydroxy group esterified with an aromatic sulfonic acid, in 2-position to the diazo group, with azo components which are coupling inorthoor vicinal position to a hydroxy or amino group, the componentschosen being of such a kind that the azo-dyestuffs contain at least oncethe grouping R -1 ICo(CHz)nSs03H (3) in which R and n have the meaningsgiven above.

As examples of diazo compounds suitable for the preparation ofmetallizable azo-dyestuffs, there may be mentioned those of thefollowing amines:

4-(,B-thiosulfato-propionyl-amino)-2-aminop|henol, 4-p-thiosulfato-propionylamino -anthranilic acid,

-(fi-thiosulfato-propionylamino)-anthranilic acid,4-(B-thiosulfato-acetylamino)-2-aminophenol, 4- or5-(thiosulfato-acetylamino)-anthranilic acid,4-(B-thiosulfato-propionylamino)-6-chloro-2- aminophenol,6-(B-thiosulfato-propionylamino)-2-aminophenol-4- sulfonic acid,2-aminophenol-4-methylsulfone, 2-aminophenol-4-propylsulfone,6-nitro-2-aminophenol-4-sulfonic acid, 6-nitro-2-aminophenol-4-sulfonicacid amide, 6-chloro-2-aminophenol-4-methylsulfone,5-chloro-Z-aminophenol-4-sulfonic acid amide,6-nitro-2-aminophenol-4-N.N-dimethyl sulfonic acid amide,2-aminophenol-4-sulfonic acid, 2-aminophenol-4-sulfonic acid amide,2-aminophenol-4-sulfonic acid-N-methylarnide, 2-aminopzhenol-4-sulfonicacid-N-ethylamide, 2-aminophenol-4-sulfonic acid-N-fi-hydroxyethylamide, 2-aminophenol-4-sulfonic acid-N-phenylamide,2-aminophenol-4sulfonic acid-NN-dimethylamide, 2-aminophenol-4-sulfonicacidN.N-di-(,B-hydroxyethyl)- amide, 4-chloro-2-aminophenol, 4- or 5- or6-nitro-2-aminophenol, 4.6-dinitro-2-aminophenol, 4-methyl-2-aminophenol, Z-aminophenol, anthranilic acid, 4- or 5- or 6-chloro-anthranilicacid, 4- or 5- or 6-nitro-anthranilic acid, 4.6-dichloro-2-aminophenol,4-nitro-6-acetylamino2-aminophenol, 2-amino-l-naphthol-4-sulfonic acidand G-nitro-Z-amino-l-naphthol-4-sulfonic acid.

As examples of azo components suitable for the preparation of themetal-free azo-dyestutfs which are used as starting compounds accordingto the invention, there may be mentioned the following groups:

acetoacetic acid arylides, pyrazolones, hydroxybenzenes,hydroxynaphthalenes and aminonaphthalenes such as 3- or4-acetoacetylamino-l-(5-thiosulfato-propionylamino)-benzene, l-(3- or4-;3-thiosulfato-propionylaminophenyl)-3- methyl-S-pyrazolone, 4-(St-uhiosulfato-propionylamino)-phenol,l-(fi-thiosulfato-propionylamino)-7-naphthol,2-(fl-thiosulfato-propionylamino)-7-naphthol,4-(fi-thiosulfato-propionylamino)-l-naphthol,2-(fl-thiosulfato-propionylamino)-6-naphthol,2-(B-thiosulfato-propionylamino)-5-hydroxynaphthalene-7-sulfonic acid,2- fl-thiosulfato-propionylamino) -8-hydroxynaphthalene-3.6-disulfonicacid,4-acetoacetylarnino-1-(N-methyl-ti-thiosulfatopropionylamino)-benzene asWell as the corresponding thiosulfato-acetylarnino compounds,furthermore, hydroxy-benzenes such as p-cresol or p-tert.-amylphenol,4-acetylamino-phenol, l-phenyl-3-metthyl-S-pyrazolone,1-phenyl-3-methyl-5-pyrazolones which are substituted in 3- or4-position by a sulfonic acid or by a sulfonic acid amide group,

l-(2-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone, l- 2',5'-dichlorophenyl -3 -methyl-5-pyrazolone,1-phenyl-5-pyrazolone-3-carboxylic acid or1-phenyl-S-pyrazolone-carboxylic acid phenylamide, barbituric acid,hydroxyquinoline, 2.3- hydroxynaphthoic acid amide,

naphthols and naphthylamines such as 6-methylor6-methoxy-2-aminonaphthalene,

Z-aminonaphthalene as such and the -aminQna hthaIenel-sulfonic acidwhich couples while splitting off the sulfonic acid group, and whichleads to the same dyestuffs as Z-aminonaphthalene, as is known,furthermore,

l-acetylamino-7-hydroxy-naphthalene,1-methane-sulfonylamino-7-hydroxy-naphthalene,l-carbethoxyamino-7-hydroxynapihthalene, S-chloroas well as5.8-dichloro-l-hydroxynaphthalene, Z-hydroxynaphthalene,

4.8- or 5.8-dichloro-l-hydroxynaphthalene, acetoacetic acid esters andacetoacetic acid amides, l-aceto acetylamino-cyclohexane,acetoacetylamino-benzene, l-acetoacetylamino-2.S-dimethyl-benzene,l-acetoacetylamino-4-methyl-benzene orl-acetoacetylamino-4-methoxy-benzene, l-acetoacetylamino-2-, -3-, or-4-chlorobenzene,

furthermore, corresponding azo components containing sulfonic acidgroups, such as l-hydroxy-naphthalene-4- or -5- sulfonic acid,

Z-acetylamino-8-hydroxynaphthalene-6-su1fonic acid,

3-acetylamino-8-hy-droxynaphthalene-6-sulfonic acid andl-acetylamino-8-hydroxynaphthalene-3.6- or -4.6-disulfonic acid.

In order to convert the azo-dyestuffs of the abovementioned Formula 1into the complex metal compounds according to method (a), the dyestuffsare treated, if desired, in mixture with one another or with othermetallizable azo-dyestuffs, with one or several metal-yielding agents,preferably, agents yielding cobalt or chromium, in a Weakly acid,neutral or weakly alkaline medium in such amounts as to obtain thecorresponding 2: l-Complex metal compounds.

As metal-yielding agents, there may be used, for example, the followinggroups: chromic fluoride, chromium sulfate, chromium formiate, chromiumacetate, potassium chromium sulfate, cobalt formiate, cobalt acetate andcobalt sulfate as well as mixtures of chromium or cobalt salts and ofalkaline metal salts of aliphatic hydroxy carboxylic acid such astartaric acid, and complex chromium compounds of aromatic ortho-hydroxycarboxylic acids such as salicylic acid.

The metallizable azo-dyestuffs can be reacted, according to theinvention, with one or several metal-yielding agents, suitably atelevated temperatures, preferably, in the range between 70 and 100 C.,in an aqueous, Weakly acid to weakly alkaline medium, if desired, in thepresence of an organic solvent such as ethanol, dioxane, glycol,monomethyl glycol or n-butanol.

It is suitable to prepare the 2: l-complex metal dyestuffs of theinvention according to method (b) by reacting a metallizableazo-dyestutf of the above-mentioned formula (1) with a 1:1-complex metaldyestuff in an aqueous, neutral to Weakly alkaline medium attemperatures ranging from about to 120 C. in a molar ratio of about 1:1.The reaction can also be carried out, if desired, in the presence of anorganic solvent which is miscible with water, for example, ethanol.

The process according to embodiment (c) can be carried out by treatingsimultaneously or successively the metallizable azo-dyestuffs of theabove-mentioned formula (2), a mixture thereof or 'a mixture of such anazo-dyestuff and another metallizable azo-dyestuifs in water or in amixture of water and of an organic solvent which is miscible with Water,under weakly acid, neutral or weakly alkaline conditions, preferably, ata pH-value ranging from 4 to 8, and at an elevated temperature,preferably, in the range of to C., with salts of the thiosulfuric acidand one or several of the metal-yielding agents mentioned above, in sudhamounts that the complex metal compounds contain two dyestutf radicalsper metal atom in complex-bound form.

It is advantageous to :prepare the dyestuffs of the invention accordingto method ((1) by reacting the 2: l-complex metal dyestuffs containing,per molecule, one or two dyestuffs of the above-mentioned Formula 2,with salts of the thiosulfuric acid in an aqueous medium or in a mixtureof water and of an organic solvent Which is miscible with water, forexample, ethanol, dioxane, ethylene glycol,

ethylene glycol monomethyl ether or ethylene glycol monoethylether, atelevated temperatures, preferably, in the range of 60 to 100 C.

The 2:1-oomplex metal compounds used as starting compounds for thisembodiment, preferably, such of cobalt or chromium, are preparedaccording to usual methods which are known per se. They can be prepared,for example, by treating metallizable azo-dyestuffs of the above-givenFormula 2, if desired, in mixture with one another or with othermetallizable azo-dyestuffs, with one or several metal-yielding agentsunder weakly acid, neutral or weakly alkaline conditions, in suchamounts as corresponds to more than 0.5, preferably, 0.5 to 0.7 atomicportion of metal per molar portion of the azo compounds to bemetallized.

As salts of the thiosulfuric acid used in the different methods of theprocess of the invention there may be mentioned the alkali metal saltsand the alkaline earth metal salts, in particular, sodium thiosulfateboth in anhydrous form and as salt containing crystal water. In general,the dyestuffs containing halogenacylamino groups, or their complex metalcompounds are reacted with the salts of the thiosulfuric acid in anequivalent ratio. In some cases, it is however advantageous to use anexcess 'amount of thiosulfate.

The metalliferous complex compounds or mixed comrplex compoundsobtainable according to the invention, which contain two dyestuffradicals per metal atom in complex-bound form, are easily soluble inwater even in the absence of sulfonic acid groups and of carboxylic acidgroups. The complex metal compounds obtained are separated from theaqueous medium by adding sodium or potassium chloride, if desired, afterelimination of the organic solvent, they are subsequently filtered off,washed, if desired, and dried. It is particularly advantageous withthose products of the invention which are very easily soluble in water,to isolate the dyestuffs by concentrating their solution in vacuo or todry them by spraying.

The metalliferous azo-dyestuffs obtainable according to the invention,are suitable for dyeing and printing materials of the most differentkind, owing to their good solubility in water. The complex metaldyestuffs which .are free from sulfonic acid groups and carboxylic acidgroups, possess an excellent affinity for nitrogen-containing materialsand are, therefore, particularly suitable for dyeing and printingnitrogenous fibers of animal and synthetic origin, such as wool, silk,leather and fibers of polyamide or of polyurethane. The wool dyeingspossess a good to excellent fastness to light and to wet processing,especially to 'washing, fulfilling, potting (severest form ofdecatizing) and to acidic cross-dyeing. The complex metal dyestuffscontaining sulfonic acid groups or carboxylic acid groups, can be usedfor dyeing and printing natural and regenerated cellulose fibers such ascotton, linen or viscose rayon.

After all, the novel complex metal dyestuffs are applied according todyeing and printing processes which are generally used in industry. Forthis purpose, they are applied, to cellulose textile, for example,according to a process used for dyeing or printing reactive dyestuffs,and they are fixed while treating them with an acid-binding agent priorto, during or after the application of the dyestuff, at usual orelevated temperatures. In order to dye textile materials containingnitrogenous fibers, such as, in particular, lwool or polyamide-fibers,the novel complex metal dyestuffs are applied to these materials, forexample, in a neutral or weakly acid dye bath having a constant ornearly constant pH-value. Dyeing is preferably carried out in thepresence of compounds that are used for dyeing nitrogenous textilematerials such as, for example, sodium sulfate, ammonium acetate,surface-active compounds such as quaternary ammonium salts and anionicdispersing agents. In this process, the pH-value of the dye bath canalso be changed during the dyeing process by adding acids or acid saltsor alkalis or alkali metal salts, for example, in such a manner as tostart the dyeing process at pH 4 and to carry it up to 7.5 during theprocess.

The novel complex metal dyestuffs have a variety of tints, for example,blue, violet, grey, orangecolored, yellow, brown and black tints. Thedeep dyeings and prints obtained with the novel dyestuffs, aredistinguished by good fastness properties, in particular, to vigorouswashing and to the action of light.

The novel complex metal dyestuffs are furthermore very stable to alkalisand have a very good solubility in water, which is maintained to itsfull extent even in the absence of sulfonic acid groups and carboxylicacid groups.

The following examples serve to illustrated the invention, but they arenot intended to limit it thereto, the parts being by weight unlessotherwise stated.

EXAMPLE 1 15.4 parts of 5-nitro-2-arninophenol were diazotized with 25parts by volume of 4 N-sodium nitrite solution in 500 parts by volume ofWater and 25 parts by volume of concentrated hydrochloric acid at 0-5 C.After the diazo solution had been adjusted to pH 7.5-8 by adding sodiumcarbonate, 37.6 parts of the potassium salt of2-([i-thiosulfato-propionylamino)-7-naphthol of the formula wereintroduced in portions. After the coupling process had been terminated,the dyestuff solution was adjusted to pH 6 with dilute hydrochloricacid, cleared in the heat and the dyestuff was isolated by salting outwith 20% of sodium chloride (referred to the volume of the solution).The humid dyestuff was dissolved together with 25 parts of chrome alumin 900 parts by volume of water, the solution was adjusted to pH 5.8-6by adding crystallized sodium acetate, and the whole was stirred underreflux condensing. The dyestuff solution was cleared in hot conditionand the dyestuff was salted out with 20% of sodium chloride and 10% ofpotassium chloride (referred to the volume of the solution). The productwas the 2: l-complex chromium compound of the dyestuff of the formulaOzN The complex metal dyestuff dyed wool and polyamides bluish greytints of very good fastness to washing and to light in a weakly acid orneutral dye bath.

The potassium salt of 2 (fl-thiosulfato-propionylamino)-7-naphthol usedas coupling component, could be prepared in the following manner:

parts of 2-(B-chloropropionylamino)-7-naphthol and 136.5 parts of sodiumthiosulfate containing crystal water, were stirred under refluxcondensing in a mixture of 800 parts by volume of ethanol and 800 partsby volume of water for 3 hours. After the ethanol had been distilled offin vacuo, the remaining aqueous solution was cleared, the reactionproduct was isolated by salting out with 20% of sodium chloride and 10%of potassium chloride (referred to the volume of the solution) and driedin vacuo at 40 C. The product contained 74-75% of the potassium salt of2-(B-thioslufato-propionylamino)- 7-naphthol.

The content of coupling component was ascertained by determining thecoupling value, for example, by reacting an aliquot part of the solutionof the reaction product with an adjusted solution of3-nitrophenyl-diazoniumchloride.

EXAMPLE 2 53.1 parts of the azo-dyestuff described in Example 1,composed of diazotized 5-nitro-2-aminophenol and 2(,B-thiosulfato-propionylarnino)-7-naphthol, and 14.2 parts of crystallizedcobalt sulfate were dissolved in 1,000 parts by volume of water. Afterthe solution had been adjusted to pH 5.8-6 by adding sodium acetate, thewhole was stirred for 2 hours at 70-80 C. The dyestuif solution wascleared in hot condition and the dyestufif was isolated by salting outwith 20% of sodium chloride (referred to the volume of the solution).The product was the 2:1-complex cobalt compound. After the usual dyeingmethods, there were obtained on wool, bluish grey tints of very goodfastness to washing and of good fastness to light.

EXAMPLE 3 53.1 parts of the dyestuff of the formula l CHz- S-SOsKobtainable by coupling diazotized S-nitroQ-aminophenol with thepotassium salt of l-(B-thiosulfato-propionylamino)-7-naphthol in aweakly alkaline solution, were reacted with 25 parts of chrome alumunder the conditions described in Example 1 and were isolated by saltingout with 20% of sodium chloride (referred to the volume of thesolution). The product was the 2:1-complex chromium compound of thedyestuff described above, and it dyed wool bluish grey tints of verygood fastness to washing and good fastness to light in a weakly acid orneutral solution.

The potassium salt of 1 ([i-thiosulfato-propionylamino)-7-naphthol usedas coupling component, could be prepared by reacting1-(fl-chloropropionylamino)-7-naphthol with sodium thiosulfate. Afterthe reaction mixture had been worked up, there was obtained an aqueoussolution from which the reaction product of the formula 1TTII-COCH2CHa-SSO3K uo@ could be isolated by salting out with 20% of sodiumchloride and 10% of potassium chloride (referred to the volume of thesolution). After drying in vacuo, there was obtained a grey powder whichcontained 68-69% of the potassium salt of 1(fi-thiosulfato-propionylamino)-7- naphthol.

EXAMPLE 4 When 53.1 parts of the dyestuif described in Example 3,paragraph 1, were treated with 14.2 parts of cobalt sulfate under theconditions described in Example 2, there was obtained after salting outwith sodium chloride the 2:1-cornplex cobalt compound of theaZo-dyestuff described in Example 3, paragraph 1, which dyed wool bluishgrey tints of very good fastness to washing and light.

8 EXAMPLE 5 COONa I III-COClI2ClIzSSOaNa obtainable by couplingdiazotized anthranilic acid with the sodium salt of1-(4-[,8thiosulfato-propionyla'mino]- phenyl)-3-methyl-5-pyrazolone, and25 parts of chrome alum were dissolved in 600 parts by volume of waterand, after the pH-value of the solution had been adjusted to 5.56 withcrystallized sodium acetate, the whole was stirred for minutes underreflux condensing. The dye stuff solution was cleared in hot conditionand the dyestuff was salted out with 20% of sodium chloride (referred tothe volume of the solution). There was obtained the 2:1-complex chromiumcompound of the dyestuff described above as a brown powder which wasvery easily soluble in water. The complex metal dyestuif showed anexcellent afiinity for wool which was dyed orange-colored tints of verygood fastness to washing and light in a weakly acid or neutral dye bath.

The sodium salt ofl-(4'-[/3thiosulfato-propionylaniinoj-phenyl)-3-rnethyl-5-pyrazoloneused as coupling component, could be prepared in the following manner:

parts of 1-(4'-[B-chloropropionylamino]-phenyl)- 3-methyl-5-pyrazoloneand 136.5 parts of sodium thiosulfate containing crystal water, werestirred under reflux condensing in a mixture of 800 parts by volume ofethanol and 800 parts by volume of water for 3 hours. After the ethanolhad been distilled off in vacuo, a small amount of a water-insolubleprecipitate separated from the aqueous phase remaining and was filteredoff. The solution obtained which contained the sodium salt of1-(4-[flthiosulfato propionylamino1-phenyl)-3-methyl-5-pyrazolone, couldbe used directly for subsequent reactions, after the content of couplingcomponent had been ascertained by determining the coupling value.

EXAMPLE 6 55.3 parts of the dyestuff of the formula obtained by couplingdiazotized anthranilic acid with the sodium salt of4-acetoacetylamino-1-( 8-thiosu1fatopropionylamino)-benzene, and 25parts of chromium alum were dissolved in 600 parts by volume of waterand, after the pH-value had been adjusted to 5 .5-6 with crystallizedsodium acetate, the whole was stirred for 90 minutes under refluxcondensing. The dyestuff solution was cleared in hot condition and thedyestuff was salted out with 20% of sodium chloride (referred to thevolume of the solution). The product was the 2: l-complex chromiumcompound of the azo compound described above. The complex metal dyestuffdyed wool neutrally yellow tints of very good fastness to Washing and tolight after the usual dyeing processes.

The sodium salt of4-acetoacetylamino-l-(fi-thiosulfato-propionylamino)-benzene used ascoupling component could be prepared in the following manner:

138 parts of 4-amino-1-(B-thiosulfato-propionylamino)- benzene presentin the form of the inner salt, were suspended in 600 parts by volume ofwater and were dissolved by adding 27 g. of anhydrous sodium carbonate.

While vigorously stirring the solution, 44 parts of diketene wereintroduced dropwise at 1520 C. while the pH- value of the solution wasmaintained at 6.5-7 by adding sodium carbonate. Subsequently, stirringwas continued for 30 minutes. The solution obtained which contained thereaction product of the formula could be used directly for subsequentreactions.

EXAMPLE 7 56.7 parts of the dyestuff of the formula which could beprepared by coupling diazotized anthranilic acid with the sodium salt of4-acetoacetylamino- (N-methyl-N-fi-thiosulfato propionyl) anilide, werereacted with 25 parts of chrome alum in the manner described in Example6, and the substance was salted out with 20% of sodium chloride(referred to the volume of the solution). The novel 2:1-complex chromiumcompound of the above-described azo-dyestulf had dyeing propertiessimilar to those of the dyestufl described in Example 6.

4-acetoacetylamino-(N-methyl-N-fi-thiosulfato propionyl)-anilide used ascoupling component, could be prepared by reacting4-amino-(N-methyl-N-fi-thiosulfatopropionylamino)-benzene with diketenein an aqueous solution.

EXAMPLE 8 176.9 parts of the sodium salt ofl-(fi-chloropropionylamino)-8naphthol-3.6-disulfonic acid and 150 partsof sodium thiosulfate containing crystal water were stirred under refluxcondensing in 1,000, parts by volume of water for 3 hours. The solutionobtained which contained the reaction product of the formula wasfiltered while still hot and filled up with Water to 1,500 parts byvolume.

18.9 parts of 2-aminopl1enol-4-sulfonic acid were diazotized with 25parts by volume of 4 N-sodium nitrite solution in 100 parts by volume ofwater and 15 parts by volume of concentrated hydrochloric acid at 5 C.After the diazonium solution had been neutralized with sodium carbonate,500 parts by volume of the solution of the reaction product describedabove, were added. After the coupling process had been terminated, thedyestuff formed was salted out with 20% of sodium chloride and 10% ofpotassium chloride (referred to the volume of the solution).

84 parts of the dyestuff obtained and 25 parts of the chrome alum weredissolved in 400 parts by volume of water. The solution was adjusted topH 6 by adding crystallized sodium acetate, and was stirred under refluxcondensing for 90 minutes. When the reaction was complete, the dyestufisolution was filtered while still hot and evaporated to dryness in vacuoat 60 C. The product NaOaS 10 was the 22l-complex chromium compound ofthe dyestuff of the formula KOgS- S 03K K There were obtained, oncotton, deep blue prints of good fastness to washing and light in thepresence of sodium carbonate.

EXAMPLE 9 67.6 parts of the dyestuff of the formula S OsNB.

densing for minutes. When the reaction was complete,

the dyestulf solution was filtered in hot condition and evaporated todryness in vacuo at 60 C. The product was the 2:1:complex chromiumcompound of the dyestuff of the formula 303K and was identical with the2:1-complex chromium dyestuff described in Example 8.

EXAMPLE 10 67.6 parts of the dyestulf of the formula OH HO NHCOCHz-CH2Cl-SOaK SOaNa and was identical with the 2:1 complex chromium dyestutfdescribed in Examples 8 and 9.

EXAMPLE 11 61.7 parts of the dyestuif of the formula (1)11 oH N=NNH-COCHzCHzSSOsNa instead of 61.7 parts of the metal-free dyestutfdescribed above, there was obtainedafter reaction with 25 parts ofchrome alum-a 2:1-complex chromium dyestutf which dyed wool greyish bluetints of good fastness to washing and light in a weakly acid or neutralbath.

EXAMPLE 12 53.5 parts of the 2: l-complex chromium compound of thedyestulr of the formula COONa (IDH w NaOaS- \/-NHCO-CH2CH2Cl and 30parts of sodium thiosulfate containing crystal water, were stirred underreflux condensing in 500 parts OzN by volume of water for 3 hours.Subsequently, the dyestufl solution was cleared in hot condition and thedyestuff was salted out with sodium chloride. The product was the2:1-complex chromium compound of the dyestuff of the formula COONa (|)HThe complex metal dyestufif dyed cotton red brown tints which showedgood fastness properties to washing and to action of light, in thepresence of sodium carbonate.

EMMPLE 13 12.5 parts of chromium triacetate of the formula Cr(C H O -H Oand 30 parts of sodium thiosulfate containing crystal water weredissolved in 800 parts by volume of water. The solution was adjusted topH 5.5-6 with sodium acetate and after an addition of 800 parts byvolume of ethanol and 40.4 parts of the dyestulf of the formula OH H Othe whole was stirred under reflux condensing for 3 hours. Subsequently,the ethanol was distilled off in vacuo and the aqueous solutionremaining was separated by filtration from a small amount of awater-insoluble residue. The 2: l-complex chromium dyestutf formed wasisolated by adding 20% of sodium chloride and 10% of potassium chloride(referred to the volume of the solution) and was dried in vacuo at 40 C.There was obtained a blackblue powder which dissolved easily in water.After the usual dyeing processes, deep violet tints of very goodfastness to washing and good fastness to light were obtained on wool.

The same dyestutf was obtained by reacting the dyestutf of the formulaOH H0 with chrome alum.

EXAMPLE 14 39.5 parts (0.1 mol) of the 1:1-comp1ex chromium compound ofthe dyestutf of the formula Z-amino-phenol with S-naphthol, and 55.3parts of the dyestutf of the formula OzN obtainable by couplingdiazotized anthranilic acid with 4-acetoacetylamino-(,li-thiosulfatopropionyl) anilide, were dissolved in a mixture of 800 parts by volumeof ethanol and 800 parts py volume of water. After the pH-value of thesolution had been adjusted to 7 by adding sodium acetate, the whole wasstirred for 3 hours under reflux condensing. Subsequently, the ethanolwas distilled off in vacuo, the aqueous solution remaining behind, wascleared in hot condition and the mixed 22lcomplex chromium dyestuff wasisolated by adding 20% of sodium chloride (referred to the volume of thesolution). The novel dyestuff dyed wool neutrally green tints of verygood fastness to washing and good fastness to light in a weakly acid orneutral dye bath.

EXAMPLE 15 48.8 parts (0.1 mol) of the lzl-complex chromium compound ofthe dyestuif of the formula OH HO NaOaS- OzN which could be prepared bycoupling l-diazo-Z-naphthol- 13 14 6-nitrosulfonic acid withfl-naphthol, and 55.3 parts of amino)-7-naphthol, 27.5 parts of thedyestufi? of the the dyestutf of the formula formula COONa COONE (DO-CH3I CO CH3 N= -N=N H which could be obtained by coupling diazotizedanthranilic acid with the sodium salt of 4-acetoacetylamino-1- obtamableby couplmg filazonzed anthrfmmc acld w(j3-thiosulfato-propionylamino)-benzene, and parts of4'acetoac6ty1amim'(fl'thlosulfato proplonyl) amhde chrome alum weredissolved in 600 parts by volume of ware dissolvpd in 1000 i by Yohlmewater After water. The solution was adjusted to pH 6 by adding thepH'value of the Sohmon had been adlusted to 7 by crystallized sodiumacetate, and was stirred for 3 hours adffing sodillm acetate the Wholewas Stirred for under reflux condensing. When the reaction was commmutesundfar reflux q i The .dyestu fi solutlon o plete, the solution wascleared in hot condition and the was filtered m hot q and the {mxedlcomPlex dyestufl. was salted out by adding 20% of sodium chloride fgdiflestufl was ateld by P (referred to the volume of the solution). Theproduct was ch e (re erred to t e 0 t so u Ion) e the mixed 2:1-complexchromium compound of both the novel dyestuff dyed 9 q q tmts of goodfast" 20 dyestutfs mentioned above. It provided, on wool, oliveness toWashmg and hght an acid bath" colored-tints of very good fastness towashing and good EXAMPLE 16 fastness tolight in a Weakly acid or neutralsolution.

When the two dyestuffs mentioned above were reacted Parts of the dyesmfiof the formula with 14.5 parts of crystallized cobalt sulfate instead ofchrome alum at pH 5.5-6 and at a temperature ranging from to C., themixed 2:1-complex cobalt com- OH OH pound of the two dyestuffs wasobtained. This product N=N provided, on wool, grey tints of very goodfastness to washing and good fastness to light after the usual dyeingO2N 30 processes.

In the following tables, there are mentioned further 0 CH2 CH**S SO1K2:1-complex metal dyestufis and their tints on wool (abbreviated in thetables with w) or on cotton (abbreviated obtainable by couplingdiazotized 5-nitro-2-amino-phenol with c) which can be preparedaccording to the emwith the potassium salt of2-(B-thiosulfato-propionyl- 35 bodiments described in the aboveexamples.

Table 1.Symmetric 2:1-complex metal dyestufis Example DiazocomponentAzocomponent Metal Tint 1 2 amino-4-nitro-benzoic acid Cr..- Red brown(w).

- NHC OOHa-CH2 SSO;H

2 An Co-.- Brown w HO- nni-o 0-orr2or12 SSO H 3 4-nitro-2-aminohenolCr-.. Currant w p no- NHCOCHz-CH2 K/ S-SO H 4 do 7 Co... Red brown w HO-NHCOOHz-CH2 S-SO3H 5 Z-aminobenzoic acid Co-.. Bluish red (w).

7 4-chloro-2-amino-phenol s 5-nitro-2-amino-phenol NH-C O-CHr-CHa Go...Blue grey (w).

| S-SOaH HO TABLE 1-Continued Example Diazoeomponent Azoeomponent MetalTint 20 .d0 OH NH-C O-GHPCHr-S-SOgH Cr. Grey blue (0).

HO3S- S 0 H 21 5-nitro-2-amlnophenol 0H 00... 'Grey blue (c and w).

NH-C O-CH2-CH2'-S-SOaH 22 do 0H 00... Blue-violet (0).

H0 8 NHC0-CH2CHz-SSO3H We claim:

1. Complex metal dyestuffs which possess in the form of the free acidsthe formula aminobenzene series, X represents a hydroxyl or group boundin ortho'position to the azo-linkage, Y represents a hydroxyl or aminogroup bound in ortho-posi tion or in vicinal position to a carbon atomattached to the azo linkage, R represents a hydrogen atom or a loweralkyl group, Me represents chromium or cobalt, stand for 1 or 2 and mstands for 0, 1 or 2.

2. The dyestuif of the formula 3. The dyestuff of the formula OzN inwhich D represents a radical of the benzeneor naphthalene-series, Arepresents the radical of an azo component of the naphthalene,pyrazolone or acetoacetyl- 25 4. The dyestufi of the formula carboxylnandm 5. The dyestufi of the formula OnN OaN

6. The dyestuif of the formula o N=N N O a References Cited UNITEDSTATES PATENTS 3,226,395 12/ 1965 Schimmelschmidt et 211.

CHARLES B. PARKER, Primary Examiner.

D. M. PAPUGA, Assistant Examiner.

US. Cl. X.R.

